CN115956000A - Method for producing functionalized organic molecules and use thereof - Google Patents

Method for producing functionalized organic molecules and use thereof Download PDF

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CN115956000A
CN115956000A CN202180046076.6A CN202180046076A CN115956000A CN 115956000 A CN115956000 A CN 115956000A CN 202180046076 A CN202180046076 A CN 202180046076A CN 115956000 A CN115956000 A CN 115956000A
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ethanol
hydroxyapatite
carried out
catalyst
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P·特伦多斯
V·桑兹贝尔特兰
A·M·罗德里格斯里韦罗
C·E·阿莱曼兰索
J·普伊加利贝拉塔
G·雷维拉-洛佩斯
J·桑斯
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Belang Surgery Co ltd
Universitat Politecnica de Catalunya UPC
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Belang Surgery Co ltd
Universitat Politecnica de Catalunya UPC
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Priority claimed from EP20382345.5A external-priority patent/EP3903911B1/en
Priority claimed from EP20382918.9A external-priority patent/EP3988523B1/en
Application filed by Belang Surgery Co ltd, Universitat Politecnica de Catalunya UPC filed Critical Belang Surgery Co ltd
Publication of CN115956000A publication Critical patent/CN115956000A/en
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    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/159—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with reducing agents other than hydrogen or hydrogen-containing gases
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    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
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    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
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    • C07C45/66—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by dehydration
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Abstract

The present invention relates to a method for producing functionalized organic molecules having 1 to 3 carbon atoms, comprising the steps of: -contacting carbon dioxide as the only gas or a gas mixture comprising or consisting of carbon dioxide and methane with a catalyst comprising or consisting of permanently polarized hydroxyapatite in the presence of water. Further, the invention relates to the use of said method.

Description

Method for producing functionalized organic molecules and use thereof
Technical Field
The present invention relates to a method for producing functionalized organic molecules, in particular functionalized organic molecules having 1 to 3 carbon atoms, and to the use thereof.
Background
Carbon dioxide (CO) 2 ) Are considered to be the main greenhouse gases and the main cause of global warming. Therefore, efficient utilization of it as a C1 feedstock for the synthesis of valuable chemical and industrial products is receiving increasing attention. For example, carbon dioxide is known to be useful as a C1 feedstock for the synthesis of ethanol (W.ZHang, Y.Hu, L.Ma, G.ZHu, Y.Wang, X.Xue, R.Chen, S.Yang.Z.jin, adv.Sci.2018,5,1700275, B.an, Z.Li, Y.Song, J.Z.ZHang, L.Z.Zeng, C.Wang, W.B.Lin, natur.Catal.2019,2,709-717 C.Liu, B.C.Col n, m.cieback, p.a.silver, d.g.nocera, science 2016,352,1210-1213 e.s.wiedner, j.c.linehan, chem.eur.j.2018,24, 16964-169971 d.wang, q.y.bi, g.h.yin, w.l.zhao, f.q.huang, x.m.xie, m.h.jiang, chem.commu.2016, 52, 14226-14229.
Further, it is known that transition metals and complexes which can act as transition metals dominate CO 2 Activation and immobilization related catalysis (c.s.yeung, angelw.chem.int.ed.2019, 58,5492-5502, c.weetman, s.inoue, chemcatchem 2018,10,4213-4228, p.p.power, nature 2010463-177, d.d.zhu, j.l.liu, s.z.adv.mater.2016,28, 3423-3452.
Due to CO 2 With the carbon atom in the highest oxidation state, CO 2 The molecules are very inert and stable. Thus, CO is converted 2 Conversion to high value chemicals having one carbon atom (C1; e.g., methanol and formic acid), two carbon atoms (C2; e.g., ethanol and acetic acid), and three carbon atoms (C3; e.g., acetone) requires very efficient electrocatalysts to promote kinetically slow CO 2 And (4) reduction process.
Therefore, there remains a further need to facilitate the CO conversion 2 A process for conversion to high value chemicals, particularly as described above.
Objects and solutions
In view of the above, it is therefore the basic object of the present invention to make available a process for the production, in particular the selective production, of functionalized organic molecules, in particular molecules having from 1 to 3 carbon atoms, which meets the needs described above.
This object is achieved by the method of independent claim 1 and by the use of claims 15 and 16. Preferred embodiments of the method are defined in the dependent claims and in the present description. The subject matter and wording of all claims, respectively, are hereby incorporated into the present description by express reference.
The present invention relates to a method for producing or synthesizing, in particular selectively producing or synthesizing, functionalized organic molecules, in particular functionalized organic molecules having 1 to 3 carbon atoms, wherein the functionalized organic molecules are preferably selected from the group consisting of ethanol, methanol, formic acid, acetic acid, malonic acid, acetone and mixtures of at least two of the aforementioned functionalized organic molecules. Preferably, the present invention relates to a process for the production or synthesis, in particular the selective production or synthesis of ethanol or a mixture comprising or consisting of ethanol and at least one further functionalized organic molecule preferably selected from methanol, formic acid, acetic acid, malonic acid and acetone, in particular to a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone, in particular wherein ethanol is the main reaction product, or to a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone, in particular wherein ethanol is the main reaction product.
The method comprises the following steps:
in the presence of water, in particular liquid water (H) 2 O), carbon dioxide (CO) as the sole gas 2 ) (i.e. carbon dioxide and no other gases) with a catalyst, in particular an electrocatalyst, comprising or consisting of permanently polarised hydroxyapatite
Or
In the presence of water, in particular liquid water (H) 2 O), carbon dioxide (CO) is included 2 ) And methane (CH) 4 ) Or consist thereof, in particular containing only carbon dioxide (CO) 2 ) And methane (CH) 4 ) Or a gas mixture consisting thereof, is contacted with a catalyst, in particular an electrocatalyst, which comprises or consists of permanently polarised hydroxyapatite.
Hereinafter, the above step of the method of the present invention is referred to as "contacting step".
As used in accordance with the present invention, the term "functionalized organic molecule" means an organic molecule that bears or comprises a functional group, i.e., a particular substituent or moiety that is generally responsible for a characteristic chemical reaction of the organic molecule. Preferably, the functional group is selected from the group consisting of carboxyl, formyl, keto, hydroxyl, and combinations thereof.
Further, as used according to the present invention, the term "functionalized organic molecule" may refer to one type of organic molecule, for example an alcohol (such as ethanol) or a carboxylic acid (such as formic acid), or to a mixture comprising or consisting of different organic molecules. For example, different organic molecules may differ in the number of carbon atoms and/or functional groups.
Preferably, the term "functionalized organic molecule" as used according to the present invention means a carboxylic acid, aldehyde, ketone, alcohol or a mixture thereof. More preferably, the one or more carboxylic acids are formic acid and/or acetic acid and/or malonic acid. The one or more ketones are preferably acetone. The one or more alcohols are preferably ethanol and/or methanol.
According to the preceding paragraph, the method according to the invention is preferably a method for producing or synthesizing, in particular selectively producing or synthesizing, carboxylic acids (in particular different carboxylic acids having 1 to 3 carbon atoms, preferably formic acid and/or acetic acid and/or malonic acid) and/or aldehydes (in particular different aldehydes having 1 to 3 carbon atoms) and/or ketones (in particular different ketones having 1 to 3 carbon atoms, preferably acetone) and/or alcohols (in particular different alcohols having 1 to 3 carbon atoms, preferably ethanol and/or methanol).
More preferably, the method according to the invention is a method for producing or synthesizing, in particular selectively producing or synthesizing, functionalized organic molecules selected from the group consisting of ethanol, methanol, formic acid, acetic acid, malonic acid, acetone and mixtures thereof, i.e. mixtures of at least two of the above functionalized organic molecules.
Particularly preferably, the method according to the invention is a method for producing or synthesizing, in particular selectively producing or synthesizing: ethanol; or a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone, in particular wherein ethanol is the main reaction product; or a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone, especially wherein ethanol is the main reaction product.
The term "main reaction product", as used according to the invention, especially in the context of ethanol, means the product with the highest molar yield in a mixture comprising or consisting of different products, especially different functionalized organic molecules, especially functionalized organic molecules having 1 to 3 carbon atoms.
As used according to the present invention, the term "permanently polarized hydroxyapatite" means a hydroxyapatite that: it undergoes a complete structural redistribution, in particular almost perfect, with a high degree of crystallinity, i.e. in particular with a small amount of amorphous calcium phosphate and the presence of vacancies and the accumulation of charges per unit of mass and surface, detected by an increase in electrochemical activity. With push not over timeThe electrochemical activity of the particles and the ion mobility are shifted away. Corresponding to permanently polarised hydroxyapatite 31 The P-NMR spectrum is shown in FIG. 1. Preferably, the profile is obtained using phosphoric acid (H) 3 PO 4 ) As a reference, with solid hydroxyapatite and shows a distinct peak at 2.6ppm corresponding to the phosphate group of the hydroxyapatite.
The term "thermally polarized hydroxyapatite" as used according to the present invention preferably means a permanently polarized hydroxyapatite obtained or obtainable by a method comprising the following steps (thermal polarization method):
(a) Sintering samples of hydroxyapatite, in particular at a temperature between 700 ℃ and 1200 ℃, and
(b) Applying a constant or variable DC voltage of between 250V and 2500V, in particular for at least 1min and/or at a temperature of between 900 ℃ and 1200 ℃, in particular between 1000 ℃ and 1200 ℃, or
Applying an equivalent field of between 1.49kV/cm and 15kV/cm, in particular for at least 1min and/or at a temperature of between 900 ℃ and 1200 ℃, in particular between 1000 ℃ and 1200 ℃, or
Applying an electrostatic discharge between 2500V-1500000V, in particular for >0min to 24h, for example for less than 10min, and/or at a temperature between 900 ℃ and 1200 ℃, in particular between 1000 ℃ and 1200 ℃, or
An equivalent electric field of between 148.9kV/cm and 8928kV/cm is applied, in particular for >0 minutes to 24 hours, for example for less than 10min, and/or at a temperature of between 900 ℃ and 1200 ℃, in particular 1000 ℃ to 1200 ℃.
The sample of hydroxyapatite in step (a) may be a sample of natural (i.e. naturally occurring) hydroxyapatite or synthetic hydroxyapatite.
Further, the sample of hydroxyapatite in step (a) may in particular be selected from a sample of crystalline hydroxyapatite, a sample of amorphous hydroxyapatite, a sample of a mixture of crystalline hydroxyapatite and amorphous calcium phosphate and mixtures thereof.
Thus, the permanently polarised hydroxyapatite of the composition or material according to the invention is preferably obtained or obtainable by the above method (thermal polarisation method).
The term "room temperature" as used according to the present invention means a temperature of 15 ℃ to 35 ℃, in particular 18 ℃ to 30 ℃, preferably 20 ℃ to 30 ℃, more preferably 20 ℃ to 28 ℃, in particular 20 ℃ to 25 ℃.
The invention is based on the surprising finding that the production or synthesis, in particular the selective production or synthesis, of functionalized organic molecules having 1 carbon atom (such as methanol and/or formic acid), functionalized organic molecules having 2 carbon atoms (such as ethanol and/or acetic acid) and functionalized organic molecules having 3 carbon atoms (such as acetone) from carbon dioxide alone or from carbon dioxide and methane in the presence of permanently polarized hydroxyapatite as catalyst can be achieved under mild conditions (in particular <10 bar pressure and. Ltoreq.250 ℃, in particular <250 ℃) at low environmental pollution levels and costs. Without wishing to be bound by theory, the generation or synthesis of functionalized organic molecules having 1 to 3 carbon atoms according to the present invention involves hydrogenation to reduce carbon dioxide and construction of a C-C bond. Thus, the method of the invention may also be denoted as an electroreduction method of carbon dioxide to carboxylic acids (such as formic acid and/or acetic acid) and/or aldehydes and/or ketones (such as acetone) and/or alcohols (such as methanol and/or ethanol), and the permanently polarized hydroxyapatite may also be denoted as an electrocatalyst.
In an embodiment of the invention, the permanently polarized hydroxyapatite comprises or has:
a crystallinity of >65%, in particular >70%, preferably >75%, more preferably 65% to 99.9%, and/or
-a proportion of amorphous calcium phosphate of <18% by weight, in particular of 0.1% by weight to 17% by weight or of <9% by weight, preferably of <5% by weight, in particular of <0.1% by weight, based on the total weight of permanently polarized hydroxyapatite,
and/or
-a proportion of beta-tricalcium phosphate of <36% by weight, in particular 0.1% by weight to 35% by weight or <12% by weight, preferably <5% by weight, in particular <0.5% by weight, based on the total weight of permanently polarized hydroxyapatite,
and/or
-10 7 Ωcm 2 -10 4 Ωcm 2 In particular 10 7 Ωcm 2 -10 5 Ωcm 2 In particular 10 6 Ωcm 2 -10 5 Ωcm 2 Preferably 10 5 Ωcm 2 And/or the bulk resistance of
A reduction in surface capacitance of less than 8%, in particular 8% to 0.1%, preferably 5% to 3%, after 3 months.
As used in accordance with the present invention, the term "bulk resistance" means resistance to electron transfer and can be determined by electrochemical impedance spectroscopy.
Preferably, the bulk resistance increases only by 0.1% to 33%, in particular 4% to 63%, preferably 4%, after 3 months.
As used according to the present invention, the term "surface capacitance" means the capacitance due to hydroxyapatite surface changes induced by the thermal polarization method and can be determined by electrochemical impedance spectroscopy.
With regard to further features and advantages of the permanently polarized hydroxyapatite as used according to the present invention, reference is made to PCT application WO 2018/024727 A1, the content of which is hereby incorporated by explicit reference.
In a further embodiment of the invention, the permanently polarized hydroxyapatite is obtained or obtainable by a method comprising the steps of:
(a) Preparing samples of hydroxyapatite, in particular crystalline hydroxyapatite,
(b) Sintering the sample prepared in step (a), in particular at a temperature between 700 ℃ and 1200 ℃,
(c) Applying a constant or variable DC voltage of between 250V and 2500V, in particular for at least 1min and/or at a temperature of between 900 ℃ and 1200 ℃, in particular between 1000 ℃ and 1200 ℃, to the sample obtained in step (b) or a shaped body thereof, or
Applying an equivalent electric field of between 1.49kV/cm and 15kV/cm, in particular for at least 1min and/or at a temperature of between 900 ℃ and 1200 ℃, in particular between 1000 ℃ and 1200 ℃, to the sample obtained in step (b) or a shaped body thereof, or
Applying an electrostatic discharge between 2500V and 1500000V, in particular for >0min to 24h, for example for less than 10min, and/or at a temperature between 900 ℃ and 1200 ℃, in particular between 1000 ℃ and 1200 ℃, or
Applying an equivalent electric field of 148.9kV/cm-8928kV/cm, in particular for >0min to 24h, for example for less than 10min, and/or at a temperature of between 900 ℃ and 1200 ℃, in particular 1000 ℃ to 1200 ℃, to the sample obtained in step (b) or to a shaped body thereof, and
(d) Cooling the sample obtained in step (c) and maintaining a DC voltage or equivalent electric field, or
Cooling the sample obtained in step (c) to maintain an electrostatic discharge or equivalent electric field, or
Cooling the sample obtained in step (c) without maintaining a DC voltage or an electrostatic discharge or equivalent electric field.
The term "sample" as used according to the present invention may particularly mean one sample, i.e. only one sample (singular), or a plurality of samples, i.e. two or more samples. The term "shaped body" as used according to the invention can therefore mean in particular one shaped body, i.e. only one shaped body (singular), or a plurality of shaped bodies, i.e. two or more shaped bodies.
The step (a) may be carried out by using diammonium phosphate (diammonium hydrogen phosphate, (NH) 4 ) 2 HPO 4 ) And calcium nitrate (Ca (NO) 3 ) 2 ) As reactants or starting materials. In particular, step (a) may be carried out by: (a) 1 ) Providing a mixture of diammonium phosphate and calcium nitrate, in particular an aqueous mixture, preferably an aqueous alcoholic mixture,
(a 2 ) Stirring step (a) 1 ) The mixture provided in (1), particularly at room temperature,
(a 3 ) For step (a) 2 ) The mixture stirred in the step (2) is subjected to hydrothermal treatment,
(a 4 ) Cooling step (a) 3 ) The mixture subjected to the hydrothermal treatment is subjected to hydrothermal treatment,
(a 5 ) Separation in step (a) 4 ) The precipitate obtained after cooling the mixture, and (a 6) a freeze-drying step (a) 5 ) To produce a hydroxyl radicalApatites, in particular crystalline hydroxyapatites.
Step (a) 1 ) This can be carried out in particular by using a mixture comprising or consisting of diammonium phosphate, calcium nitrate, water (in particular deionized water), ethanol and optionally a chelated calcium solution. Advantageously, the pH of the mixture and/or the pH of the aqueous calcium nitrate solution used to provide the mixture may be adjusted to 10-12, preferably 10.5. Thus, the shape and size of the hydroxyapatite can be controlled, particularly in the form of nanoparticles. Further, step (a) 2 ) It may be carried out under agitation, in particular mild agitation, for example using 150rpm to 400rpm. Further, step (a) 2 ) It can also be carried out for 1min to 12h, in particular for 1h. According to the invention, step (a) 2 ) Also referred to as an aging step. Further, step (a) 3 ) It can be carried out at a temperature of from 60 ℃ to 240 ℃, preferably 150 ℃. Further, step (a) 3 ) It can be carried out at a pressure of from 1 bar to 250 bar, preferably 20 bar. Further, step (a) 3 ) Can be carried out for 0.1h to 72h, preferably 24h. Further, step (a) 4 ) Can be prepared by mixing step (a) 3 ) The hydrothermal treatment is carried out by cooling the mixture to 0 ℃ to 90 ℃, in particular to 25 ℃. Further, step (a) 5 ) This may be done by centrifugation and/or filtration. Further, in the step (a) of carrying out 6 ) Before, the washing step (a) 5 ) In particular using water and/or a mixture of ethanol and water. Further, step (a) 6 ) It may be carried out for 1 to 4 days, in particular for 2 to 3 days, preferably for 3 days.
Further, the above step (b) may be carried out at a temperature of between 700 ℃ and 1150 ℃, particularly between 800 ℃ and 1100 ℃, particularly 1000 ℃.
Further, the method preferably comprises a further step (bc) between step (b) and step (c):
-pressing the sample obtained in step (b) to form a shaped body or to form a shaped body thereof, i.e. to form a shaped body of the sample obtained in step (b).
In particular, step (bc) can be carried out at a pressure of from 1MPa to 1000 MPa, in particular from 100MPa to 800 MPa, preferably from 600MPa to 700 MPa. Further, step (bc) may be carried out for 1min to 90min, in particular for 5min to 50min, preferably for 10min to 30min.
The shaped bodies can have a polygonal (for example triangular, square or rectangular, pentagonal, hexagonal, heptagonal, octagonal or nonagonal) or non-angular (in particular circular, oval or elliptical) cross section. Further, the thickness of the shaped body may be >0cm to 10cm, in particular >0cm to 5cm, preferably >0cm to 2cm. In particular, the thickness of the shaped bodies may be from 0.1cm to 10cm, in particular from 0.1cm to 5cm, preferably from 0.5cm to 2cm.
Preferably, the shaped body is in the form of a disc, plate, cone or cylinder.
Advantageously, by carrying out step (c), a catalytic activation of the sample obtained in step (b) or of the shaped body thereof can be achieved. Preferably, step (c) is carried out by placing the sample obtained in step (b) or its shaped body between a positive electrode and a negative electrode, wherein the sample obtained in step (b) or its shaped body is in contact with both electrodes. For example, the electrodes may be in the form of stainless steel plates, in particular stainless steel AISI 304 plates. Further, the electrodes may have a mutual distance of 0.01mm to 10cm, in particular 0.01mm to 5cm, preferably 0.01mm to 1mm.
The electrodes may have different shapes. The electrodes may have a polygonal cross-section (e.g. square or rectangular) or a non-angular (in particular circular, oval or elliptical) cross-section. In particular, the thickness of the electrode may be >0cm to 10cm, in particular >0cm to 5cm, preferably >0cm to 1mm. For example, the electrodes may be in the form of disks, plates, or cylinders.
Further, in the above step (c) a constant or variable DC voltage or equivalent electric field may be applied for 1h-24h, in particular 0.1h-10h, in particular 1h.
Further, the DC voltage applied in the above step (c) is preferably 500V, which is equivalent to a constant electric field of 3kV/cm.
Further, the equivalent electric field applied in the above step (c) is preferably 3kV/cm.
Further, the temperature in the above step (c) is preferably at least 900 ℃, more preferably at least 1000 ℃. Preferably, the temperature in step (c) is from 900 ℃ to 1200 ℃, in particular from 1000 ℃ to 1200 ℃, in particular 1000 ℃.
Preferably, step (c) is carried out by applying a constant or variable DC voltage of 500V at 1000 ℃ to the sample obtained in step (b) or a shaped body thereof, in particular a discotic shaped body, for 1 hour.
Further, the above step (d) may be carried out by cooling the sample obtained in the step (c) to room temperature.
Further, the above step (d) may be carried out for 1min to 72h, in particular 15min to 5h, preferably 15min to 2h.
In a further embodiment of the invention, the permanently polarized hydroxyapatite is obtained or obtainable by a method comprising the steps of:
(a) Preparation of samples of hydroxyapatite, in particular of crystalline hydroxyapatite, in particular using diammonium phosphate (diammonium hydrogen phosphate, (NH) 4 ) 2 HPO 4 ) And calcium nitrate (Ca (NO) 3 ) 2 ) As a result of the use of the reactants or starting materials,
(b) Sintering the sample prepared in step (a), in particular at a temperature of 1000 ℃, in particular for 2h,
(c) Applying an equivalent electric field of 3kV/cm, in particular at a temperature of 1000 ℃, in particular for 1h, to the sample obtained in step (b) or to a shaped body thereof, and
(d) Cooling the sample obtained in step (c) maintaining the equivalent electric field, in particular for 30min.
With regard to further features and advantages of steps (a) - (d), reference is made in its entirety to the previous description.
In a further embodiment of the present invention, the contacting step is carried out in the presence of liquid water and/or water vapor. In other words, according to a further embodiment of the present invention, the water is in liquid form and/or in vapour form, for carrying out the contacting step.
In a further embodiment of the invention, the contacting step is carried out at a volume ratio of 1000 to 0.01, in particular 500 to 1, preferably 300.
In a further embodiment of the invention, the contacting step is carried out with carbon dioxide alone.
In a further embodiment of the invention, the contacting step is carried out with a volume ratio of carbon dioxide to methane of 200.
In a further embodiment of the invention, the contacting step is carried out at a total pressure of from 0.1 bar to 100 bar, in particular from 0.1 bar to 10 bar, in particular from 1 bar to 8 bar, in particular from 1 bar to 6 bar, preferably 6 bar.
As used in accordance with the present invention, the term "total pressure" refers to the carbon dioxide pressure (when the gas is used alone) or to the sum of the partial pressures of each gas in the gas mixture, preferably at room temperature.
In a further embodiment of the invention, the contacting step is carried out at a carbon dioxide pressure of from 0.035 bar to 90 bar, in particular from 0.1 bar to 10 bar, in particular from 1 bar to 8 bar, preferably 6 bar.
In a further embodiment of the invention, the contacting step is carried out at a partial pressure of carbon dioxide of from 0.035 bar to 90 bar, in particular from 0.1 bar to 3 bar, in particular from 1 bar to 3 bar, preferably 3 bar, and/or at a partial pressure of methane of from 0.00017 bar to 5 bar, in particular from 1 bar to 3 bar, preferably 3 bar.
Further, the contacting step may be carried out in the presence of a catalyst and water, in particular liquid water, at a total pressure of the gas mixture of from 0.0001 bar to 250 bar.
Further, the contacting step may be conducted in the presence of a catalyst at a carbon dioxide to methane pressure ratio (CO) 2 :CH 4 ) At a bar of 0.0001 to 250 and 0.0001.
Further, the gas mixture may in particular be nitrogen (N) free 2 ). In other words, the contacting step may be carried out in the absence of nitrogen.
In a further embodiment of the invention, the contacting step is carried out with a molar ratio of carbon dioxide to permanently polarized hydroxyapatite of 0.1 to 0.5, in particular 0.2 to 0.5, preferably 0.3 to 0.5.
In a further embodiment of the invention, the contacting step is carried out with a molar ratio of methane to permanently polarized hydroxyapatite of between 0.1 and 0.5, in particular between 0.2 and 0.5, preferably between 0.3 and 0.5.
Preferably, the contacting step is carried out by using uncoated, permanently polarised hydroxyapatite, i.e. by using permanently polarised hydroxyapatite lacking any coating. In this respect, it was surprisingly finally found that the use of uncoated, permanently polarized hydroxyapatite advantageously significantly increases the conversion of carbon dioxide into functionalized organic molecules having 2 and/or 3 carbon atoms (such as ethanol and/or acetic acid and/or acetone) and in particular additionally maximizes the selective synthesis of ethanol as the main reaction product. Similarly, the use of uncoated, permanently polarised hydroxyapatite advantageously significantly increases the conversion of carbon dioxide and methane to ethanol, and in particular additionally maximizes the selective synthesis of ethanol as the main reaction product.
Alternatively, the contacting step may be carried out by using coated permanently polarised hydroxyapatite. In principle, the contacting step can be carried out by using a coating such as TiO 2 、MgO 2 、MnO 2 Or a combination thereof, or the like. More specifically, the contacting step can be carried out by using permanently polarized hydroxyapatite with three layers of coating, in particular wherein the three layers of coating can be formed by two layers of aminotri (methylenephosphonic acid) and one layer of zirconium oxychloride (ZrOCl) 2 ) Or zirconium oxide ZrO 2 In which the zirconium oxychloride layer is arranged or sandwiched between two layers of aminotri (methylenephosphonic acid). The reaction efficiency can be advantageously increased by using coated permanently polarised hydroxyapatite.
In a further embodiment of the invention, the contacting step is carried out under UV (ultraviolet) irradiation or UV-Vis (ultraviolet-visible) irradiation. In particular, the contacting step may be carried out under UV radiation or UV-Vis radiation at a wavelength of from 200nm to 850nm, in particular from 240nm to 400nm, preferably from 250nm to 260nm, more preferably 253.7 nm. Further, the contacting step may especially be carried out under UV radiation having a wavelength of 200nm to 280nm, especially 240nm to 270nm, preferably 250nm to 260nm, more preferably 253.7 nm. Preferably, the permanently polarized hydroxyapatite is directly exposed to or irradiated with UV radiation or UV-Vis radiation. Advantageously, the UV radiation or UV-Vis radiation is provided by a suitable UV source and/or Vis source (e.g. a UV lamp and/or a Vis lamp).
In further embodiments of the invention, the contacting step is conducted at an irradiance of 0.1W/m 2 -200 W/m 2 In particular 1W/m 2 -50 W/m 2 Preferably 2W/m 2 -10 W/m 2 More preferably 3W/m 2 Under UV (ultraviolet) radiation or UV-Vis (ultraviolet-visible) radiation. With regard to the advantages of this embodiment, reference is made to the preceding paragraphs.
In a further embodiment of the invention, the contacting step is carried out at a temperature of from 25 ℃ to 250 ℃, in particular from 95 ℃ to 140 ℃, preferably 95 ℃.
More preferably, the contacting step is carried out at a temperature of 95 ℃ and under UV irradiation. These reaction conditions are particularly suitable for the synthesis, in particular the selective synthesis, of functionalized organic molecules having 2 carbon atoms (such as ethanol and/or acetic acid) in high yields.
Further, the contacting step may preferably be carried out without UV irradiation and at a temperature of 25 ℃ to 250 ℃, in particular 95 ℃ to 140 ℃, preferably 140 ℃. Moreover, the reaction conditions according to this embodiment lead to the synthesis, in particular the selective synthesis, of functionalized organic molecules having 2 carbon atoms (such as ethanol and/or acetic acid) in high yields.
Further, the contacting step may be carried out for 0.0001h to 120h, in particular for 24h to 72h, preferably for 48h to 72h.
Further, the process, in particular the contacting step, may be carried out continuously or discontinuously, in particular as a batch process.
Further, the contacting step may be carried out by using air, in particular traffic polluted air, as the gas mixture. Thus, functionalized organic molecules having 1 to 3 carbon atoms, in particular ethanol and/or acetic acid and/or methanol and/or formic acid and/or acetone, can be synthesized as valuable compounds and at the same time carbon dioxide can be removed from the air, in particular traffic polluted air.
Preferably, the method comprises the further steps of:
-isolating and/or separating off and/or purifying the functionalized organic molecule obtained during or in the contacting step.
The above further steps are preferably carried out by dissolving and extracting the catalyst and/or by extracting the supernatant formed during or in the contacting step.
In a further embodiment of the invention, the method is used for the production or synthesis, in particular the selective production or synthesis of ethanol.
In a further embodiment of the invention, the method is used to produce or synthesize a mixture comprising or consisting of ethanol and at least one further functionalized organic molecule preferably selected from methanol, formic acid, acetic acid, malonic acid and acetone.
More preferably, the method is used to produce or synthesize a mixture comprising or consisting of ethanol and at least one further functionalized organic molecule selected from methanol, formic acid, acetic acid and acetone.
Alternatively, the method is preferably used to produce or synthesize a mixture comprising or consisting of ethanol and at least one additional functionalized organic molecule selected from methanol, acetic acid, malonic acid and acetone.
In a further embodiment of the invention, the process is used to produce or synthesize a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone.
In a further embodiment of the invention, the method is used to produce or synthesize a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone.
Further, the present invention relates to the use of the method according to the invention for removing carbon dioxide from the atmosphere, in particular from the air (i.e. the earth's atmosphere). In particular, the present invention relates to the use of the method according to the present invention for removing carbon dioxide from contaminated (poluted) or polluted (contaminated) air, such as traffic contaminated air.
As used in accordance with the present invention, the term "air" or "earth's atmosphere" means a layer of gas retained by earth's gravitational forces, surrounding and forming the planet's atmosphere.
Further features and advantages with regard to use, reference is made in their entirety to the previous description.
Finally, the invention relates to the use of a method comprising the following steps for the generation or synthesis, in particular the selective generation or synthesis, of organic molecules, in particular organic molecules having 1 to 3 carbon atoms, wherein the functionalized organic molecules are preferably selected from the group consisting of ethanol, methanol, formic acid, acetic acid, malonic acid, acetone and mixtures of at least two of the aforementioned functionalized organic molecules:
in the presence of water, in particular liquid water (H) 2 O), carbon dioxide (CO) as the sole gas 2 ) (i.e. carbon dioxide and no other gases) with a catalyst, in particular an electrocatalyst, comprising or consisting of permanently polarised hydroxyapatite
Or
In the presence of water, in particular liquid water (H) 2 O), carbon dioxide (CO) is included 2 ) And methane (CH) 4 ) Or consist thereof, in particular containing only carbon dioxide (CO) 2 ) And methane (CH) 4 ) Or consists thereof, is contacted with a catalyst, in particular an electrocatalyst, which comprises or consists of permanently polarised hydroxyapatite.
Preferably, the use of the method is for producing or synthesizing, in particular selectively producing or synthesizing, ethanol or a mixture comprising or consisting of ethanol and at least one further functionalized organic molecule selected from methanol, formic acid, acetic acid, malonic acid and acetone, in particular to a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone, in particular wherein ethanol is the predominant reaction product, or to a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone, in particular wherein ethanol is the predominant reaction product. With regard to further features and advantages of use, in particular in respect of the process and the functionalized organic molecules, reference is made in its entirety to the previous description.
Further features and advantages of the invention will become apparent from the following examples, taken in conjunction with the subject matter of the dependent claims. In one embodiment of the invention, the individual features can be realized individually or in several combinations. The preferred embodiments are only for illustration and a better understanding of the present invention and should not be construed as limiting the present invention in any way.
Description of the drawings
For a better understanding of the disclosure, the attached drawings show, schematically or by way of illustration and by way of non-limiting example only, a practical situation of an embodiment of the invention.
FIG. 1 shows diagrammatically the preparation of permanently polarised hydroxyapatite (p-HAp) according to the invention 31 P-NMR spectrum.
FIG. 2 (a) schematically depicts a pair of 930-990cm -1 V within interval 1 Peak raman spectrum of deconvoluted hydroxyapatite (HAp) samples. Counts (a.u.) are plotted on the ordinate. Raman shift (cm) -1 ) Plotted on the abscissa.
FIG. 2 (b) schematically depicts a pair of 930-990cm -1 V within the interval 1 Peak raman spectra of deconvoluted, permanently polarized hydroxyapatite (HAp) samples. Counts (a.u.) are plotted on the ordinate. Raman shift (cm) -1 ) Plotted on the abscissa.
Comparing 930-990cm before and after Hap polarization -1 Raman v within interval 1 Fig. 2 (a) - (b) of the peaks demonstrate the success of the polarization method.
The area of HAp, amorphous Calcium Phosphate (ACP) and β -tricalcium phosphate (β -TCP) indicate the content of each phase. The content of coexisting phases underwent a reduction in the polarized samples (i.e., ACP and β -TCP of 4.3% and 9.8%, respectively) with a full width at half maximum (FWHM) from 9cm of HAp -1 Down to 5cm of p-HAp -1 . The result indicates that the HAp phase is reduced by, for example, PO 4 3- Crystal imperfections such as tetrahedral distortion increase.
Figure 3 (a) shows a scanning electron microscopy micrograph of permanently polarised hydroxyapatite. Thus, permanently polarized hydroxyapatite can be described as particles of (about) 100nm-300nm that aggregate to form aggregates of up to 1 μm in size.
FIG. 3 (b) is a diagram showing the solution obtained after the extraction of the reaction product of the reaction 1 H-NMR spectrum, using CO in the presence of conventional (i.e. non-polarised) hydroxyapatite as catalyst at 95 ℃ under UV radiation 2 (3 bar), CH 4 (3 bar), H 2 O (1 mL) for 72h. The reaction catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
FIG. 3 (c) is a diagram showing the solution obtained after the extraction of the reaction product of the reaction 1 H-NMR spectrum, said reaction using CO as catalyst at 95 ℃ under UV radiation using (uncoated) permanently polarised hydroxyapatite 2 (3 bar), CH 4 (3 bar), H 2 O (1 mL) for 72h. The reaction catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
FIG. 3 (d) is a diagram showing the solution obtained after the extraction of the reaction product of the reaction 1 H-NMR spectrum, said reaction using CO in the presence of coated p-HAp 2 (3 bar), CH 4 (3 bar), H 2 O (1 mL) for 72h. Using aminotri (methylenephosphonic acid) (hereinafter referred to as ATMP) and zirconium oxychloride (ZrOCl) at 95 ℃ under UV radiation 2 ) (hereinafter referred to as ZC) coating p-HAp. The reaction catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
As shown in fig. 3 (b) - (d), the chemical shifts observed after dissolution of the coated p-HAp are slightly unmasked with respect to the peaks of the product derived from the uncoated catalyst. This effect has been attributed to amino tris (methylene phosphonic Acid) (ATMP), which increases the acidity of the medium,
resulting in a low field shift that is not detected for p-HAp and HAp, regardless of the condition. On the other hand, fig. 3 (b) - (c) indicate that removal of the coating from the catalyst not only increases the conversion to ethanol by 20%, but also maximizes the selective synthesis of ethanol as the primary reaction product.
FIG. 4 (a) shows graphically a further of the solution obtained after extraction of the reaction product 1 H-NMR spectrum of the reaction product from CO using (uncoated) permanently polarised hydroxyapatite as catalyst and 95 ℃ and UV radiation as reaction conditions 2 (3 bar), CH 4 (3 bar) and H 2 O (1 mL) was obtained after 72h. Dissolving the catalyst in a solution containing 100mM HCl and 50mM NaCl in water.
FIG. 4 (b) is a diagram showing the solution obtained after the extraction of the reaction product 1 H-NMR spectrum of the reaction product from CO using (uncoated) permanently polarised hydroxyapatite as catalyst and 95 ℃ without UV radiation as reaction conditions 2 (3 bar), CH 4 (3 bar) and H 2 O (1 mL) was obtained after 72h. The catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
FIG. 4 (c) is a diagram showing the solution obtained after the extraction of the reaction product 1 H-NMR spectrum of the reaction product from CO using permanently polarised hydroxyapatite as catalyst and 140 ℃ without UV radiation as reaction conditions 2 (3 bar), CH 4 (3 bar) and H 2 O (1 mL) was obtained after 72h. The catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
FIG. 4 (d) shows graphically the reaction conditions at 95 ℃ with UV radiation from CO using (uncoated) permanently polarized hydroxyapatite as catalyst and UV radiation 2 (3 bar), CH 4 (3 bar) and H 2 Additional of liquid Water O (1 mL) after 72h of reaction 1 H-NMR spectrum. The pattern was cut to avoid a very intense water peak at 4.7 ppm.
FIG. 4 (e) shows graphically a further solution obtained after extraction of the reaction product 1 H-NMR spectrum of the reaction product from CO using (uncoated) permanently polarised hydroxyapatite as catalyst and 95 ℃ and UV radiation as reaction conditions 2 (3 bar), CH 4 (3 bar) and H 2 O (1 mL) was obtained after 72h. The catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl. The pattern was cut to avoid a very strong water peak at 4.7 ppm.
The spectrum shows that methanol and formic acid appear as reaction products in the liquid water used for the reaction. Ethanol and acetic acid were present in both the catalyst and liquid water, whereas acetone was detected only in the former.
FIG. 5 shows diagrammatically 3 protonated forms of CO 2 Adsorption molecule in permanently polarized hydroxyapatite OH - Representation on empty bits. Numerical value (in)eV) represents the calculated adsorption energy.
To support the p-HAp immobilization mechanism based on carboxylate formation, DFT calculations were performed at the PBE-D3 level. Consider the (0001) facet (facet) as the most stable HAp surface, and consider H among them 2 The calculation was performed using an iso-bond model as a proton source. The 3 different CO's were calculated by inserting the molecule into the hydroxyl vacancy of the mineral 2 Adsorption energy of the protonated product. The results demonstrate that CO 2 Protonation to formic acid is exothermic in the gas phase, at-3.1 kcal/mol, but is more exothermic when adsorbed on the p-HAp substrate, at-32.7 kcal/mol. However, all protonated species show endothermic adsorption energy, with the adsorption energy of protonated formic acid being very small (0.2 kcal/mol), while CO is 2 The adsorption energy of (a) is 5.1kcal/ml (as shown in some representative cases in FIG. 5, examining other sites on the p-HAp shows higher energy), thus making it impossible to follow the path completely and transfer the catalytic site to elsewhere in proximity.
FIG. 6 shows, by way of a diagram, a further of the solution obtained after extraction of the reaction product 1 H-NMR spectrum of the reaction product from CO in the presence of permanently polarised hydroxyapatite coated with aminotris (methylenephosphonic acid) and zirconium oxychloride under UV radiation at 95 DEG C 2 (3 bar), CH 4 (3 bar) and H 2 O (1 mL) was obtained after 72h. The reaction catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl. The spectrum includes an OH band at 4.65 ppm.
FIG. 7 shows graphically the evolution of CO from 95 ℃ with UV radiation (control 1) and without UV radiation (control 2) 2 (3 bar), CH 4 (3 bar) and H 2 Of O (1 mL) in liquid water after 72h 1 H-NMR spectrum. No catalyst was used for the reaction.
FIG. 8 (a) shows the CO evolution at 95 ℃ using UV radiation and (uncoated) permanently polarised hydroxyapatite as catalyst 2 (3 bar), CH 4 (3 bar) and H 2 Additional of O (1 mL) reaction product obtained after 72h 1 H-NMR spectrum in which analysis of the solution obtained after product extraction was carried out by dissolving the catalyst with 100mM HCl and 50mM NaCl.
FIG. 8 (b) shows graphically the formation of CO from a mixture of UV radiation at 95 ℃ and a (uncoated) permanently polarised hydroxyapatite as catalyst 2 (3 bar), CH 4 (3 bar) and H 2 Of the reaction product obtained after 72h O (1 mL) 1 H-NMR spectra in which the liquid water which has been incorporated into the reaction chamber has been analysed.
FIG. 9 (a) shows graphically the use of UV radiation at 95 ℃ and (uncoated) permanently polarized hydroxyapatite as catalyst from CO in the absence of water 2 (3 bar) and CH 4 (3 bar) of the reaction product obtained after 72h 1 H-NMR spectrum.
FIG. 9 (b) shows graphically the use of UV radiation and (uncoated) permanently polarized hydroxyapatite as catalyst at 95 ℃ with excess water, from CO 2 (3 bar) and CH 4 (3 bar) of the reaction product obtained after 72h 1 H-NMR spectrum.
FIG. 10 shows diagrammatically the solution obtained after extraction of the reaction product 1 H-NMR spectrum of the reaction product at 95 ℃ and under UV radiation from polluted air (atmospheric pressure) and H at 95 ℃ using (uncoated) permanently polarized hydroxyapatite as catalyst 2 Obtained after 72h in O (1 mL). The reaction catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
FIG. 11 (a) shows graphically the conversion of CO from (uncoated) permanently polarised hydroxyapatite as catalyst and 140 ℃ as reaction conditions (without UV radiation) 2 (6 bar) and H 2 Additional of liquid Water after O (1 mL) reaction for 48h 1 H-NMR spectrum. The pattern was cut to avoid a very strong water peak at 4.7 ppm.
FIG. 11 (b) shows graphically a further of the solution obtained after extraction of the reaction product 1 H-NMR spectrum of the reaction product from CO using (uncoated) permanently polarised hydroxyapatite as catalyst and 140 ℃ as reaction conditions (no UV radiation) 2 (6 bar) and H 2 O (1 mL) was obtained after 48h. The catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl. The pattern was cut to avoid a very strong water peak at 4.7 ppm.
The spectra show methanol, formic acid, ethanol, acetic acid and acetone as reaction products in both liquid water and catalyst and liquid water. The yield in liquid water (μmol/g catalyst) was: 0.21 + -0.07 (methanol), 2.44 + -0.97 (formic acid), 4.50 + -0.91 (ethanol), 2.22 + -0.88 (acetic acid) and 0.74 + -0.15 (acetone). The yield in the catalyst (μmol/g catalyst) was: 0.56 + -0.19 (methanol), 3.22 + -0.54 (formic acid), 6.60 + -2.32 (ethanol), 0.49 + -0.12 (acetic acid) and 0.62 + -0.27 (acetone).
FIG. 12 (a) shows graphically, e.g., by using CO at 140 deg.C (without UV radiation) 2 (1, 2, 4 or 6 bar) and H 2 Of O (1 mL) of the solution obtained after extraction of the reaction product obtained after 48h 1 Yields of ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) (expressed as. Mu. Mol product/g catalyst) relative to CO determined by HNMR spectroscopy 2 Variation of pressure (in bar). The catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
Figure 12 (b) shows graphically from liquid water, e.g. by using (uncoated) permanently polarised hydroxyapatite as catalyst 1 H NMR spectra measured the yields of ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) (expressed as. Mu. Mol product/g catalyst) relative to CO 2 Variation of pressure (in bar). In all cases, the reaction was carried out at 140 ℃ with CO (without UV radiation) 2 (1, 2, 4 or 6 bar) and H 2 O (1 mL) for 48h.
FIG. 12 (c) graphically shows the sum of the yields (expressed as μmol product/g catalyst) obtained from the solutions obtained after extraction of the reaction products ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) from the catalyst (FIG. 12 a) and the supernatant (FIG. 12 b) relative to CO 2 Variation of pressure (in bar). In all cases, the reaction was carried out at 140 ℃ with CO (without UV radiation) 2 (1, 2, 4 or 6 bar) and H 2 O (1 mL) for 48h.
FIG. 12 (d) shows graphically the extraction of the reaction products C1 (methanol and formic acid; meOH + HCOOH), C2 (ethanol) from the catalyst (FIG. 12 a) and the supernatant (FIG. 12 b)And acetic acid; etOH + AcOH) and C3 (acetone; ace) obtained in solution (expressed as. Mu. Mol product/g catalyst) in total yield relative to CO 2 Variation of pressure (in bar). In all cases, the reaction was carried out at 140 ℃ with CO (without UV radiation) 2 (1, 2, 4 or 6 bar) and H 2 O (1 mL) for 48h.
FIG. 13 (a) shows graphically the use of CO as an extract at 95, 120 or 140 deg.C (without UV radiation) 2 (6 bar) and H 2 Of O (1 mL) in a solution obtained after 48h of the reaction product obtained 1 H NMR spectroscopy determines the change in yield (expressed as μmol product/g catalyst) of ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) with respect to temperature (expressed in ° c). The catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
FIG. 13 (b) shows graphically the conversion from liquid water, e.g. by using (uncoated) permanently polarised hydroxyapatite as catalyst 1 H NMR spectroscopy determines the change in yield (expressed as μmol product/g catalyst) of ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) with respect to temperature (expressed in ° c). In all cases, the reaction was carried out at 95, 120 or 140 ℃ with CO (without UV radiation) 2 (6 bar) and H 2 O (1 mL) for 48h.
Fig. 13 (c) shows graphically the sum of the yields (expressed as μmol product/g catalyst) obtained from the solutions obtained after extraction of the reaction products ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) from the catalyst (fig. 13 a) and the supernatant (fig. 13 b) versus the temperature (expressed in ° c). In all cases, the reaction was carried out at 95, 120 or 140 ℃ with CO (without UV radiation) 2 (6 bar) and H 2 O (1 mL) for 48h.
FIG. 13 (d) shows graphically the sum of the yields (expressed as. Mu. Mol product/g catalyst) obtained from the solutions obtained after extraction of the reaction products C1 (methanol and formic acid; meOH + HCOOH), C2 (ethanol and acetic acid; etOH + AcOH) and C3 (acetone; ace) from the catalyst (FIG. 13 a) and the supernatant (FIG. 13 b) versus the temperature (expressed in ℃ C.). In all cases, the reaction is carried out at 95, 120 or 140 ℃ ((C))No UV radiation) using CO 2 (6 bar) and H 2 O (1 mL) for 48h.
FIG. 14 (a) shows graphically the use of CO at 140 deg.C (without UV radiation) as by extraction 2 (6 bar) and H 2 O (1 mL) of a solution obtained after 24, 48 and 72h of the reaction product obtained 1 H NMR spectroscopy measured the change in the yield (expressed as μmol product/g catalyst) of ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) versus the reaction time (expressed in hours). The catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
FIG. 14 (b) shows graphically the conversion of water from liquid water, e.g. by using (uncoated) permanently polarized hydroxyapatite as catalyst 1 H NMR spectroscopy measured the yield (expressed as μmol product/g catalyst) of ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) versus time (expressed in hours). In all cases, the reaction was carried out at 140 ℃ with CO (without UV radiation) 2 (6 bar) and H 2 O (1 mL) for 24, 48 or 72h.
Fig. 14 (c) shows graphically the total sum of the yields (expressed as μmol product/g catalyst) obtained from the solutions obtained after extraction of the reaction products ethanol (EtOH), acetic acid (AcOH), methanol (MeOH), formic acid (HCOOH) and acetone (Ace) from the catalyst (fig. 14 a) and the supernatant (fig. 14 b) versus time (expressed in hours). In all cases, the reaction was carried out at 140 ℃ with CO (without UV radiation) 2 (6 bar) and H 2 O (1 mL) for 24, 48 or 72h.
FIG. 14 (d) shows graphically the sum of the yields (expressed as μmol product/g catalyst) obtained from the solutions obtained after extraction of the reaction products C1 (methanol and formic acid; meOH + HCOOH), C2 (ethanol and acetic acid; etOH + AcOH) and C3 (acetone; ace) from the catalyst (FIG. 14 a) and the supernatant (FIG. 14 b) over time (expressed in hours). In all cases, the reaction was carried out at 140 ℃ with CO (without UV radiation) 2 (6 bar) and H 2 O (1 mL) for 24, 48 or 72h.
FIG. 15 shows diagrammatically the solution obtained after extraction of the reaction product 1 H-NMR spectrum ofReaction product at 95 ℃ and under UV radiation Using (uncoated) permanently polarized hydroxyapatite as catalyst, from contaminated air (atmospheric pressure) and H at 95 ℃ 2 Obtained after 72h in O (1 mL). The reaction catalyst was dissolved in an aqueous solution containing 100mM HCl and 50mM NaCl.
Experimental part
1. Material
Calcium nitrate (Ca (NO) 3 ) 2 ) Diammonium hydrogen phosphate ((NH) 4 ) 2 HPO 4 (ii) a Purity of>99.0%) and 30% ammonium hydroxide solution (NH) 4 OH; purity: 28-30% w/w) was purchased from Sigma Aldrich. Ethanol (purity)>99.5%) from Scharlab. All experiments were performed with milli-Q water.
2. Hydrothermal synthesis of hydroxyapatite (HAp)
15mL of 0.5M (NH) in deionized water 4 ) 2 HPO 4 At 2mL min -1 To 25mL of 0.5M Ca (NO) in ethanol 3 ) 2 In (previously pH adjusted to 10.5 using ammonium hydroxide solution) and aged for 1h. The whole process was carried out under mild agitation (150 rpm) and at room temperature. Hydrothermal treatment was applied at 150 ℃ for 24h using autoclave Digestec DAB-2. The autoclave was allowed to cool before opening. The precipitate was separated by centrifugation and washed with water and 60/40v/v ethanol-water mixture (twice). After freeze-drying it for 3 days, the resulting white powder was sintered for 2h in air at 1000 ℃ using a Carbolite ELF11/6W/301 furnace.
3. Thermal shock polarization method (TSP)
Mechanically consistent disks with a thickness of about 1.5mm were obtained by pressing 150mg of previously sintered HAp powder at 620MPa for 10 minutes. The HAp disks were placed between two stainless steels (AISI 304) and the thermal polarization was completed using the same laboratory furnace as above, with a GAMMA power supply applied at 1000 ℃ for 1h at 1000 ℃ with 3kV/cm. The pan was allowed to cool, the applied potential was maintained for 30 minutes, and finally all systems were shut down and allowed to cool overnight.
4. Characterization of
Vibrational spectra of structural fingerprints were obtained by inVia Qontor confocal raman microscope (Renishaw) equipped with a Renishaw Centrus 2957T2 detector and a 785nm laser.
SEM images were obtained using a Zeiss Neon n 40 microscope equipped with SEM GEMINI columns. HRTEM was performed in a JEOL 2010F microscope equipped with a field emission electron source, and operated at an acceleration voltage of 200 kV. The point-to-point resolution was 0.19nm and the line-to-line resolution was 0.14nm. The sample was dispersed in an alcohol suspension in an ultrasonic bath and a drop of the suspension was placed on a grid with a porous carbon film. The images are not filtered or processed by digital processing and they correspond to the raw data. All of 1 H-NMR spectra were all acquired on a Bruker Avance III-400 spectrometer operating at 400.1MHz and accumulating 64 scans. Chemical shift calibration was performed using tetramethylsilane as an internal standard. The sample was dissolved in milli-Q water containing 100mM HCl and 50mM NaCl and finally deuterated water was added.
5. Details of the calculation
The 2x 1x 2HAp supercell was chosen to construct the (0001) facet of p-HAp. The latter is achieved by removing OH orthogonal to the surface from the HAp super cell - To construct, the super cell was previously optimized at the selected DFT level. Thus, all calculations apply a +1 global charge, taking into account unpaired spins if necessary, except for calculations involving formate. The initial coordinates of the HAp are optimized to release the surface tension in accordance with the computational details provided below. A plane wave method implemented with a Quantum espress 4.6 open source computer code suite is used. Applying default C 6 Software coefficients, calculated at theoretical PBE levels corrected for grime trisomy interaction potential (PBE-D3). The kinetic energy cut-off value of the 40Ry wave function is used. A k-point mesh of 3x 3x 1 is automatically generated. In contrast, a gamma-centered 1x 1x 1k grid was used for the computation of discrete molecules, while a 7 x 7k grid was used for the overall HAp computation. Geometric optimization using conjugate gradient algorithm until the energy and force changes between successive steps are below 10, respectively -3 a.u and 10 -4 and a.u. Optimizing the energy of each step until the deviation from self-consistency is less than 10 -5 And Ry. Adsorption energy was calculated according to the following method: a + S → AS * Wherein A is an adsorbate; s is surface and AS * Is in an adsorbed state. Adsorption energy (E) ads ) Is represented by E ads ＝E AS* -(E A +E s )。
6. Reaction chamber
All reactions were carried out using a specially designed high pressure stainless steel reactor. Briefly, the reactor was interspersed with pressure gauges, electric heaters with thermocouples and external temperature controllers. The reactor also features an inert reaction chamber coated with perfluoropolymer (Teflon, 120 mL) into which both catalyst and water are incorporated. The reactor was equipped with 3 independent inlet valves for the incorporation of gas and one outlet valve for the recovery of gaseous reaction products. A UV lamp (GPH 265T5L/4, 253.7 nm) was also placed in the middle of the reactor to irradiate the catalyst directly, the lamp being protected by a UV transparent quartz tube. All surfaces are coated with a thin film of perfluoropolymer (Teflon) to avoid any contact between the reaction medium and the reactor surfaces, in such a way as to eliminate other catalyst effects.
7. Synthesis of coated p-HAp
By immersion in the corresponding aqueous solution at room temperature for 5h, a three-layer system consisting of successive depositions of aminotris (methylenephosphonic Acid) (ATMP) and zirconium oxychloride (ZC) on p-HAp was obtained. To deposit the first ATMP layer, the p-HAp was immersed in a 5mM ATMP solution for 5h. Subsequently, the p-HAp was laminated by dipping ATMP into 5mM ZrOCl 2 ZC was deposited in solution for 5h onto the p-HAp of an ATMP stack. Finally, a second layer of ATMP was deposited on the p-HAp of the ZC and ATMP stacks by dipping the p-HAp of the ATMP stacks in a 1.25mM ATMP solution for 5h.
8. Synthesis of functionalized organic molecules with 1-3 carbon atoms using uncoated p-HAp as catalyst
In the presence of uncoated p-HAp as catalyst and in the presence of liquid H 2 In the case of O (1 mL), from CO alone 2 Gas (1, 2, 4 or 6 bar) and CO 2 And CH 4 The gas mixture (3 bar each) was used to synthesize functionalized organic molecules having 1-3 carbon atoms. The reaction was carried out at 95, 120 or 140 ℃ and under irradiation with UV lamps (GPH 265T5L/4, 253.7 nm) directly irradiating the uncoated p-HAp or without UV radiation for 24, 48 or 72h.
As a representative example of the reactionTo the following yields (expressed as μmol product/g catalyst): reaction at 95 ℃ with CO under UV irradiation 2 (3 bar), CH 4 (3 bar) and H 2 O (1 mL) for 72h.
Yield obtained by dissolving the catalyst from the solution obtained after extraction: ethanol (19.4 + -3.8 μmol/g), acetone (0.9 + -0.1 μmol/g) and acetic acid (0.6 + -0.1 μmol/g). Methanol and formic acid were not detected.
Yield from liquid water (supernatant): ethanol (0.7 + -0.14. Mu. Mol/g), acetic acid (2.0 + -0.5. Mu. Mol/g), methanol (1.5 + -0.3. Mu. Mol/g) and formic acid (1.9 + -0.6. Mu. Mol/g). Acetone was not detected.
Reaction at 140 ℃ with CO in the absence of UV radiation 2 (6 bar) and H 2 O (1 mL) for 48h.
Yield obtained by dissolving the catalyst from the solution obtained after extraction: ethanol (6.6 + -2.3. Mu. Mol/g), formic acid (3.2 + -0.5. Mu. Mol/g), acetone (0.6 + -0.3. Mu. Mol/g), methanol (0.6 + -0.2. Mu. Mol/g) and acetic acid (0.5 + -0.1. Mu. Mol/g).
Yield from liquid water (supernatant): ethanol (4.5 + -0.9 μmol/g), formic acid (2.4 + -1.0 μmol/g), acetic acid (2.2 + -0.9 μmol/g), acetone (0.7 + -0.1 μmol/g), and methanol (0.2 + -0.1 μmol/g).
Reaction at 140 ℃ with CO in the absence of UV radiation 2 (1 bar) and H 2 O (1 mL) for 48h.
Yield obtained by dissolving the catalyst from the solution obtained after extraction: acetone (1.6 + -0.6 μmol/g), formic acid (1.1 + -0.3 μmol/g), ethanol (0.8 + -0.2 μmol/g), acetic acid (0.8 + -0.2 μmol/g) and methanol (0.5 + -0.2 μmol/g).
Yield from liquid water (supernatant): acetic acid (2.4 + -1.0 μmol/g), (1.3 + -0.3 μmol/g), formic acid (1.1 + -0.3 μmol/g), acetone (0.8 + -0.3 μmol/g), ethanol (0.8 + -0.1 μmol/g) and methanol (0.1 + -0.03 μmol/g).
Reaction at 95 ℃ with CO in the absence of UV radiation 2 (6 bar) and H 2 O (1 mL) for 48h.
Yield obtained from the solution obtained after extraction by dissolving the catalyst: formic acid (1.1. + -. 0.3. Mu. Mol/g), ethanol (0.7. + -. 0.3. Mu. Mol/g), acetone (0.6. + -. 0.2. Mu. Mol/g), acetic acid (0.5. + -. 0.1. Mu. Mol/g) and methanol (0.3. + -. 0.1. Mu. Mol/g).
Yield from liquid water (supernatant): acetic acid (4.6 + -0.6 μmol/g), acetone (2.3 + -0.3 μmol/g), formic acid (1.1 + -0.1 μmol/g) and ethanol (0.4 + -0.1 μmol/g). Methanol was not detected.
Reaction at 140 ℃ with CO in the absence of UV radiation 2 (6 bar) and H 2 O (1 mL) for 72h.
Yield obtained from the solution obtained after extraction by dissolving the catalyst: ethanol (10.2 + -3.0 μmol/g), formic acid (2.4 + -0.5 μmol/g), acetone (0.9 + -0.2 μmol/g), acetic acid (0.7 + -0.2 μmol/g) and methanol (0.6 + -0.2 μmol/g).
Yield from liquid water (supernatant): ethanol (7.0 + -1.1 μmol/g), acetic acid (3.0 + -1.2 μmol/g), formic acid (1.9 + -0.8 μmol/g), acetone (1.1 + -0.4 μmol/g) and methanol (0.2 + -0.1 μmol/g).
9. Synthesis of functionalized organic molecules with 1-3 carbon atoms using coated p-HAp as catalyst
In the presence of coated p-HAp as catalyst and in the presence of liquid H 2 In the case of O (1 mL), the reaction is carried out with CO 2 And CH 4 The gas mixture (3 bar each) was used to synthesize functionalized organic molecules having 1-3 carbon atoms. The reaction was carried out at 95 ℃ and under irradiation with UV lamps (GPH 265T5L/4, 253.7 nm) which directly irradiated the coated p-HAp for 72h. p-HA is coated with two layers of aminotri (methylenephosphonic acid) and one layer of zirconium oxychloride (ZrOCl) 2 ) Wherein the zirconium oxychloride layer is arranged or sandwiched between two layers of aminotris (methylenephosphonic acid). The yield obtained by dissolving the catalyst from the solution obtained after extraction (expressed as μmol product/g coated p-HAp) was: ethanol (16.1 + -3.2 μmol/g), methanol (4.9 + -1.0 μmol/g), acetone (0.8 + -0.2 μmol/g) and acetic acid (0.6 + -0.1 μmol/g).
10. Synthesis of ethanol using coated p-HAp as catalyst
In the presence of coated p-HAp as catalyst and in the presence of liquid H 2 In the case of O (1 mL), the catalyst is prepared from CO 2 And CH 4 Gas mixture (each of)3 bar) to synthesize ethanol. The reaction was carried out at 95 ℃ and under irradiation with UV lamps (GPH 265T5L/4, 253.7 nm) which directly irradiated the coated p-HAp for 72h. p-HA is coated with two layers of aminotri (methylenephosphonic acid) and one layer of zirconium oxychloride (ZrOCl) 2 ) Wherein the zirconium oxychloride layer is arranged or sandwiched between two layers of aminotris (methylenephosphonic acid). The reaction resulted in the following yields (expressed as μmol product/g coated p-HAp): ethanol (16.1 + -3.2 μmol/g), methanol (4.9 + -1.0 μmol/g), malonic acid (1.6 + -0.2 μmol/g), acetone (0.8 + -0.2 μmol/g) and acetic acid (0.6 + -0.1 μmol/g). Not only by quartet (CH) at 3.53ppm and 1.06ppm, respectively 2 ) And triplet (CH) 3 ) And passes a strong OH peak at 4.65ppm whereby 1 The H-NMR spectrum identifies the major product, ethanol.
11. Synthesis of ethanol Using (uncoated) HAp as catalyst in the Presence of (uncoated) HAp as catalyst and in the Presence of liquid H 2 In the case of O (1 mL), the catalyst is prepared from CO 2 And CH 4 Gas mixtures (3 bar each) were used to synthesize ethanol. The reaction was carried out at 95 ℃ and under irradiation with UV lamps (GPH 265T5L/4, 253.7 nm) which directly irradiate the p-HAp for 72h. The reaction resulted in very poor ethanol yields (1.9. + -. 0.5. Mu. Mol/g catalyst). Further, the yields of acetone and acetic acid<0.1. Mu. Mol/g catalyst.
12. Synthesis of ethanol without solid support as catalyst in the presence of (uncoated) HAp as catalyst and in the presence of liquid H 2 In the case of O (1 mL), the reaction is carried out with CO 2 And CH 4 The gas mixture (3 bar each) was used to synthesize ethanol. The reaction was carried out at 95 ℃ and under irradiation with UV lamp (GPH 265T5L/4, 253.7 nm) for 72h. In the absence of any solid support acting as a catalyst (see FIG. 7 (a)), the yield of ethanol was practically 0 (0.1. + -. 0.05. Mu. Mol/g). CO that has been attributed to eventual photoinduction 2 This small amount of reduction and water splitting disappears completely in the absence of UV radiation (see 7 (b)).
13. Synthesis of functionalized organic molecules with 1-3 carbon atoms, in particular ethanol, using traffic polluted air
As a proof of concept, the reaction for the synthesis of ethanol was carried out at atmospheric pressure using a catalyst obtained from BarcelolPolluted air in an area around the eastern school of the UPC (Universal Potolite de Catalunanya), which is heavily polluted by automobile traffic because it is in front of one of the major roads in the city. CO contained in air contaminated by combustion of fossil recarburisers 2 And CH 4 Significantly above the average of ambient air. The reaction was carried out in the presence of 1mL of water and at 95 ℃ with UV irradiation using p-Hap as catalyst. Analysis of the reaction products after 72h showed ethanol, etc., some of which were not found in the previous reaction with the controlled gas mixture. Although the amounts of ethanol (1.1. + -. 0.2. Mu. Mol/g), acetic acid (0.03. + -. 0.01. Mu. Mol/g), acetone (0.09. + -. 0.02. Mu. Mol/g), formic acid (0.13. + -. 0.05. Mu. Mol/g) and methanol (0.16. + -. 0.04. Mu. Mol/g) are very small, it was found that the formation of high value chemicals confirms the potential applicability of p-HAp as a catalyst regeneration to contaminate air while yielding functionalized organic molecules having 1 to 3 carbon atoms as valuable products.
14. Further study of mechanistic pathways
The formation of functionalized organic molecules having 1-3 carbon atoms may be related to the pressure, temperature and reaction time of the feed gas. To explore the role of the reaction conditions, CO was used 2 The gas and uncoated p-HAp as catalysts repeat the process without UV irradiation. As shown in fig. 12 (a) - (d), the yield of functionalized organic molecules having 1-3 carbon atoms increases with pressure. When the pressure was increased from 1 to 6 bar, the total yield (sum of yields of each product by dissolving the catalyst + sum of yields of each product from the supernatant) increased from 11.9 ± 1.6 to 23.1 ± 2.3 μmol/g.
In summary, it can be demonstrated that permanently polarized hydroxyapatite converts gaseous CO following an electroreduction mechanism 2 Are catalytic activities of high value organic chemicals, i.e., functionalized organic molecules having 1-3 carbon atoms. Experiments under different reaction conditions reflect the formation of functionalized organic molecules with 1-3 carbon atoms induced by permanently polarized hydroxyapatite CO 2 Is formed by electroreduction. As a proof of concept, the proposed reaction has successfully obtained high-value chemical products from road traffic polluted air, and opens up aAn exciting new road to convert greenhouse gas emissions into valuable chemical products using simple catalysts based on earth-rich minerals.

Claims (16)

1. Method for producing functionalized organic molecules having 1 to 3 carbon atoms, in particular selected from ethanol, methanol, formic acid, acetic acid, malonic acid, acetone and mixtures of at least two of the above functionalized organic molecules, comprising the following steps:
-contacting carbon dioxide as the only gas or a gas mixture comprising or consisting of carbon dioxide and methane with a catalyst comprising or consisting of permanently polarized hydroxyapatite in the presence of water.
2. Method according to claim 1, characterized in that said permanently polarised hydroxyapatite has:
a crystallinity of >65%, in particular >70%, preferably >75%, more preferably 65% to 99%, and/or
-a proportion of amorphous calcium phosphate of <18% by weight, in particular from 0.1% by weight to 17% by weight, based on the total weight of the permanently polarized hydroxyapatite, and/or
-beta-tricalcium phosphate in a proportion of <36% by weight, in particular 0.1% by weight to 35% by weight, based on the total weight of the permanently polarized hydroxyapatite, and/or
-10 7 Ωcm 2 -10 5 Ωcm 2 In particular 10 6 Ωcm 2 -10 5 Ωcm 2 Wherein the bulk resistance preferably increases only by 4% to 73%, in particular 4% to 63%, preferably 4%, and/or after 3 months
-a reduction in surface capacitance of less than 8%, in particular 8% -0.1%, preferably 5% -3%, after 3 months.
3. Method according to claim 1 or 2, characterized in that said permanently polarised hydroxyapatite is obtained by a method comprising the following steps:
(a) A sample of the hydroxyapatite was prepared and,
(b) Sintering the sample prepared in step (a) at a temperature between 700 ℃ and 1200 ℃,
(c) Applying a constant or variable DC voltage of between 250V and 2500V, in particular at a temperature of between 900 ℃ and 1200 ℃, to the sample obtained in step (b) or a shaped body thereof for at least 1min, or
Applying an equivalent electric field of between 1.49kV/cm and 15kV/cm, in particular at a temperature of between 900 ℃ and 1200 ℃, to the sample obtained in step (b) or to a shaped body thereof for at least 1min, or
Applying an electrostatic discharge of between 2500V and 1500000V, in particular at a temperature of between 900 ℃ and 1200 ℃, for less than 10min, or
Applying an equivalent electric field of 148.9kV/cm-8928kV/cm, in particular at a temperature between 900 ℃ and 1200 ℃, to the sample obtained in step (b) or its shaped body, and
(d) Cooling the sample obtained in step (c) maintaining said DC voltage or said equivalent electric field, or
Cooling the sample obtained in step (c) with or without maintaining said electrostatic discharge or said equivalent electric field.
4. Method according to any one of the preceding claims, characterized in that said permanently polarised hydroxyapatite is obtained by a method comprising the following steps:
(a) A sample of the hydroxyapatite was prepared and,
(b) Sintering the sample prepared in step (a) at a temperature of 1000 ℃, in particular for 2h,
(c) Applying an equivalent electric field of 3kV/cm, in particular for 1h, to the sample obtained in step (b) or to a shaped body thereof at a temperature of 1000 ℃, and
(d) Cooling the sample obtained in step (c) and maintaining said equivalent electric field, in particular for 30 minutes.
5. The method according to any of the preceding claims, characterized in that said contacting step is carried out in the presence of liquid water.
6. The method according to any one of the preceding claims, characterized in that the contacting step is carried out at a volume ratio of 1000 to 0.01, in particular 500 to 1, preferably 300 to 350.
7. The process according to any one of the preceding claims, characterized in that said contacting step is carried out at a volume ratio of carbon dioxide to methane of 200, in particular 3, preferably 1.
8. The process according to any one of the preceding claims, characterized in that said contacting step is carried out at a total pressure of 0.1 bar to 100 bar, in particular 1 bar to 10 bar, preferably 6 bar.
9. The process according to any one of the preceding claims, characterized in that said contacting step is carried out at a carbon dioxide pressure of 0.035 to 100 bar, in particular 1 to 6 bar, preferably 6 bar.
10. The process according to any one of the preceding claims, characterized in that said contacting step is carried out at a partial pressure of carbon dioxide ranging from 0.035 to 90 bar, in particular from 1 bar to 3 bar, preferably 3 bar, and/or at a partial pressure of methane ranging from 0.00017 bar to 5 bar, in particular from 1 bar to 3 bar, preferably 3 bar.
11. The method according to any one of the preceding claims, characterized in that the contacting step is carried out with a molar ratio of carbon dioxide to permanently polarized hydroxyapatite of 0.1 to 0.5, in particular 0.2 to 0.5, preferably 0.3 to 0.5 and/or with a molar ratio of methane to permanently polarized hydroxyapatite of 0.1 to 0.5, in particular 0.2 to 0.5, preferably 0.3 to 0.5.
12. The process according to any one of the preceding claims, characterized in that the contacting step is carried out under UV-irradiation or UV-Vis-irradiation at a wavelength of 200nm to 850nm, in particular 240nm to 400nm, preferably 250nm to 260nm, more preferably 253.7 nm.
13. The method according to any one of the preceding claims, characterized in that the contacting step is carried out under UV irradiation or visible light irradiation, in particular with 0.1W/m 2 -200
W/m 2 In particular 1W/m 2 -50 W/m 2 Preferably 2W/m 2 -10 W/m 2 Irradiance of (c).
14. The process according to any one of the preceding claims, characterized in that said contacting step is carried out at a temperature of 25 ℃ to 250 ℃, in particular 95 ℃ to 140 ℃, preferably 95 ℃.
15. Use of a method according to any of the preceding claims for producing: ethanol; or a mixture comprising or consisting of ethanol and at least one other functionalized organic molecule selected from methanol, formic acid, acetic acid, malonic acid and acetone; or a mixture comprising or consisting of ethanol, methanol, formic acid, acetic acid and acetone, in particular wherein ethanol is the main reaction product; or a mixture comprising or consisting of ethanol, methanol, acetic acid, malonic acid and acetone, especially wherein ethanol is the main reaction product.
16. Use of a method according to any one of the preceding claims for removing carbon dioxide from the atmosphere.
CN202180046076.6A 2020-04-28 2021-04-27 Method for producing functionalized organic molecules and use thereof Pending CN115956000A (en)

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